1. Field of the Invention
This invention relates to a color image forming process and a silver halide photographic light-sensitive material utilizing a novel 2-equivalent magenta color-forming coupler (also referred to herein simply as the "magenta coupler").
2. Description of the Prior Art
It is known that, upon color development of a silver halide color photograhic material, an oxidized aromatic primary amine color developing agent reacts with a coupler to form an indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine or like dye, thereby forming color images. In such a system, color reproduction is usually based on subtractive color photography, and silver halide emulsions selectively sensitive to blue, green and red light, respectively, and yellow, magenta and cyan color image-forming compounds which are in a complementary color relation to the sensitivity of the respective emulsions are employed. For example, acylacetanilide or dibenzoylmethane couplers are generally used for the formation of a yellow color image; pyrazolone, pyrazolobenzimidazole, cyanoacetophenone and indazolone couplers are generally used for the formation of magenta color images, and phenolic couplers (e.g., phenols and naphthols) are generally used for the formation of cyan color images.
In one of the most preferred embodiments of color photographic light-sensitive materials, dye image-forming couplers are added to silver halide emulsions. Couplers added to emulsions must be rendered nondiffusible (or diffusion-resistant) in a binder matrix of the emulsions.
Most conventional color image-forming couplers are 4-equivalent couplers. That is, the development of 4 mols of silver halide as an oxidizing agent is theoretically necessary to form 1 mol of dye through the coupling reaction. On the other hand, 2-equivalent couplers are also known, having an active methylene group substituted with a group (often referred to as a "coupling-off" group) eliminatable upon oxidative coupling of the coupler with an oxidation product of an aromatic primary amine developing agent. Such 2-equivalent couplers require the development of only 2 mols of silver halide to form 1 mol of dye. Since 2-equivalent couplers require only one-half the silver halide as compared with conventional 4-equivalent couplers to form a dye, their use enables rapid processing of light-sensitive materials due to the thinness of the light-sensitive layer, improvement of the photographic properties due to a reduction in film thickness, and results in economic advantages.
Several approaches have thus far been suggested to produce 2-equivalent 5-pyrazolone couplers (primarily for use as magenta-forming couplers). For example, the substitution of the 4-position of a pyrazolone with a thiocyano group is described in U.S. Pat. Nos. 3,214,437 and 3,253,924, with an acyloxy group is described in U.S. Pat. No. 3,311,476, with an aryloxy group is described in U.S. Pat. No. 3,419,391, with a 2-triazolyl group is described in U.S. Pat. No. 3,617,291, and with a halogen atom is described in U.S. Pat. No. 3,522,052.
However, in using these 4-position substituted pyrazolone couplers, there are disadvantages, e.g., serious color fog may result; the reactivity of the couplers may be unsuitable; the couplers may be chemically so unstable that they are converted to materials incapable of color formation with the lapse of time; or synthesis of the couplers is often difficult.
Also, it has hitherto been known to substitute the 4-position of a 5-pyrazolone with an alkylthio group, an arylthio group or a heterocyclic ring thio group, as described in U.S. Pat. No. 3,227,554. However, with many of these known thio-substituted pyrazolone compounds, the reactivity with the oxidation product of an aromatic primary amino color developing agent is unsuitable and, further, they are difficult to employ in ordinary color light-sensitive materials due to the strong photographic action of the mercapto compound produced as a result of the coupling reaction. In addition, the chemical stability of these couplers is not generally satisfactory.
Further, pyrazole type magenta couplers having an arylthio group or an alkylthio group at the 4-position thereof and an acyloxy group or a sulfonyloxy group at the 5-position thereof are disclosed in Japanese Patent Application (OPI) No. 80744/79 (the term "OPI" as used herein refers to a "published unexamined Japanese patent application"). These 4-position thio-substituted pyrazole compounds show improved stability to formalin gas in comparison with the corresponding 4-equivalent couplers. Although these pyrazole compounds have good stability to a certain degree in comparison with the corresponding 4-position thio-substituted pyrazolone compounds, they are still insufficient for practical use. Therefore, compounds having higher stability have been desired. Also, these known compounds show only small improvements in the increase of sensitivity. Furthermore, these compounds have certain restrictions to utilize in ordinary color light-sensitive materials since the problems such as effects to other photographic layers, contamination of color development processing solutions, etc., due to the photographic action of the mercapto compound produced as a result of the coupling reaction are accompanied.
Recently, 2-equivalent 5-pyrazolone magenta couplers having a heterocyclic substituent at the 4-position thereof have been disclosed in some patents. For example, an imidazolyl group and a derivative thereof, a 1,2,4-triazolyl group and a derivative thereof and a 1,2,3-triazolyl group and a derivative thereof are described in German Patent Application (OLS) No. 2,536,191, and a 1,2,4-triazolyl group and a derivative thereof are described in German Patent Application (OLS) No. 2,651,363.
The compounds described in the above-mentioned patents show good color-forming properties, and thus satisfy one of the characteristics required of 2-equivalent magenta couplers. However, those couplers having an imidazolyl group or a 1,2,4-triazolyl group still also have some disadvantages. For example, their use is accompanied by a decrease in the sensitivity of the silver halide due to interaction with the silver halide (for example, by adsorption onto the light-sensitive center of silver halide, etc.) and the chemical stability of these couplers is not satisfactory. Furthermore, many 2-equivalent 5-pyrazolone magenta couplers having a heterocyclic substituent at the 4-position thereof have a low solubility to an organic solvent and thus, in certain case, it is incapable of dispersing these couplers in a silver halide emulsion. Therefore, the increase in solubility of couplers is recently one of the important problems with respect to 2-equivalent magenta couplers as well as the improvement in photographic properties.